Method of producing colored photographic materials



June 30, 1936. B;VGASPAR n 2,046,067

METHOD OF PRODUCING COLORED PHOTOGRAPHIC MATERIALS Filed Deo. l, 1932 Patented June 30, 1936 rares 'PATENT OFFICE METHOD F PRGDUCENG COLORED PHOTOGRAPHC MATERIALS Bela Gaspar, Brussels, Belgium 3 Claims.

This invention relates to a method of producing colored photographic materials.

The invention may be illustrated diagrammatically by Figures 1, 2, 3 and 4 in the accompanying drawing, which shows several forms of embodiment.

In Figure l, c represents the carrier or support, whilst b is a silver bromide gelatine layer colored, for example, with Chrysophenine G (36e), which has been precipitated with hydrochlorid 2-pheny14aminoquinoline In Figure 2, c is the carrier or support, b an uncolored silver bromide gelatine layer, and a; a gelatine layer colored, for example, with Chrysophenine G (304i), which has been precipitated with hydrochloric 2-phenyl-4-aminoquinoline.

Figure 3 shows a similar material to Figure 2 with reverse order oi the layers c and b, that is to say--a is applied to the support and b situated over e.

Figure 4 shows a form of embodiment having three dierently colored silver bromide layers. c is a backing or support of desired material, and d, e and f are silver bromide gelatine layers colcred as follows:-

d contains Diamine pure blue FF (424),4 e Chrysophenine G 3de. and ,f Amidonaphthol red 6B (66). Each of these dyestuffs is precipitated in the emulsion by 'Z-phenyl--aminoquinoline The index numbers for the dyestuis given in the abovev refer to the Schultz Dyestuif Tables, 5th Ed., 1920.

It is already known for the purpose of producing color photographs to incorporate dyestuffs in photographic layers and to fix these by a mor- 'danting process or by the formation of a deposit. in this connection, however, it has been. found that various dyestufs reveal the tendency to separate again subsequently from the mordant. Be- 40 yond this, the inorganic salts proposed for this purpose, such as alkaline earth or heavy metal salts are very disturbing in the layer, as the same may readily react with the photographic bath or take eiect on the silver halide.

It has been found that diffusion of the dyestufs in the layer may be prevented to a very considerable extent, if salts of the acid or substantive dyestuils, and more particularly of the sulphonic acids of these dyestuis, are introduced into the layer with nitrogenous organic bases. These substances also have no detrimental eiiect on the silver halide.

The salts in question may be incorporated in finished state in the layers or emulsions in nnesuspension or by way of addition in a mutable solvent, for example alcohol, or these deposits may be produced in the layer itself by double decomposition. These non-diffusing salts of the dvestuf may be incorporated in those layers, which consist of a plurality of part layers poured 5 one over the other or of a plurality of particles lsuch as result from the known re-emulsifying action of diierently colored emulsions. They may also be formed by applying, atomizing or impressing the dyestui on to a colloidal layer, l0 whereby there is employed eithera solution of the dyestu salts, or the same may be employed together with the organic bases for coloring the arrangements as described, or the dvestuif deposit may be formed in the layer itself by way '15 of double decomposition. This method of xing dyestui's may also be employed for other purposes, for example in the transfer method, in which, for example, an organic base is introduced into the colloid used for the transfer, and an insoluble non-diffusing salt of the dyestui there formed after the transfer has taken place. In this method the transfer images are extremely sharp, owing to prevention of the dilusion. This method is also extremely useful for the pro- 25 duction of anti-halo layers.

Layers containing, for example, substantive dyes, which may be removed entirely from the gelatine by Washing, may be applied to the emulsion carrier on the front or the rear side of a film or plate or immediately above or below the emulsion.

For this purpose there is produced the suitable salt of an organic base, for example 2-phenyl-4- aminoquinoline, with Ponceau 4R. This salt may be split in a caustic alkaline developer and the dyestuii thereupon removed by washing.

The resulting salts possess varying powers of dissociation, and it is desirable for color photographic purposes to employ a merely weak alkaline neutral or acid developer.

Eampies 1. A 1% solution of Diamine pure blue FF (518) is admired with a solution of guanidine sulphate. A deposit is formed, which is ltered.

2. Metanil yellow (138) is admixed with hydrochloric Z-phenyl-a-amino-quinoline.

The number of useful salt forming organic bases is extremely large. It is also possible to 'employ alkaloids, for instance quinine or cinchonine. The dyestufl isbrought together with a salt of the bases in a solution and the resulting deposit .subsequently dissolved in alcohol or another suitable solvent and added to the gelatine. 55

, above lsalts to the rest of the gelatine.

The procedure may also be such that the dyestui'i is added to'a part of the gelatine and one of the 0r the layer may contain the bases and subsequently be colored with vdyestuii, or, vice versa, the dyestufr may b e included in the layer, and subsequently treated with a base for the purpose of producing the dyestui! deposit.

3. A'colorless gelatine solution is admixed with au alcoholic solution of hydrochloric 2phenyl4 amino-quinoline, and a ne grain suspension of the quinoline salt is caused. The gelatine is poured onto paper, and transfer images, for example pina type images, formed on the layers thus produced. 'Ihe resulting pictures ar, extremely sharp, owing to the lack oi' diffusion.

Whatl I claim is:-

l. In ys. method of producing colored multilayer photographic materials in which at least one colored emulsion is poured onto a support, the step which consists in coloring the emulsion by a water insoluble salt of an acid festui and a colorless nitrogeno organic base produced at a point in the process prior to coating by double decomposition of a water soluble salt of said colorless nitrogenous organic base and a water soluble salt of the said acid dyestuii. V

2. In a method of producing colored multilayer photographic materials in which at least one colored light-sensitive emulsion is poured onto a support, the step which consists in coloring the emulsion by a water insoluble salt of an acid dyestui! and a colorless nitrogenous organic base produced in the emulsion at a point in the process prior to coating by double decomposition of a water soluble salt of said colorless nitrogenous organic base and a' water soluble base of the said acid dyestuil'.

3. A photographic material consisting of a support and at least two superimposed layers,

wherein at least one layer contains a substantially water insoluble salt of a colorless nitroge- 2 0 nous organic base and an acid dyestun.

BLA GASPAR. 

